Asphalt compositions



United States Patent ASPHALT COMPOSITIONS Mathew L. Kalinowski, Chicago,and Lowell T. Crews, Homewood, 111., assignors to Standard Oil Company,Chicago, 111., a corporation of Indiana No Drawing. Application July 30,E54, Serial No. 446,964

Claims. (Cl. 106273) The present invention is directed to improvementsin bitumen compositions, and particularly to improvements in mineralaggregate coating compositions, and more particularly relates to bitumencompositions having improved adherence to damp or wet mineralaggregates, and to improvements in the method of making suchcompositions.

Residual oils and/ or bituminous materials used in the preparation ofpavements and roads do not coat and adhere well to mineral aggregatesunless the aggregate is substantially dry, and for this reason, inconventional pavements or road construction practice, it is customary todry the mineral aggregate by suitable well known methods. Furthermore,water entering the road or pavement during service may have adetrimental effect in that it may displace the oil or bitumen from thesurface of the aggregate and thus diminish the bonding eifect of the oiland/or bitumen. This materially shortens the life of the road orpavement requiring frequent repairs and is,

therefore, uneconomical.

Mineral aggregates employed in road or pavement con struction range incharacter from hydrophilic to hydrophobic. In general, siliceous andacidic minerals, such as sands and gravels, tend to be hydrophobic,while calcareous alkaline minerals, such as limestone, tend to behydrophilic. It has been observed that the mineral aggregates appear tohave a greater attraction for water than for oil or bitumens and that itis diflicult to obtain, by conventional methods, complete orsatisfactory coating of aggregates by oil or bitumen when water ispresent. Furthermore, even though satisfactory coating is obtained byusing dry aggregate, the oil or bitumen tends to be displaced if waterenters the pavement or road.

It is known that the coating of damp or wet mineral aggregates by oil orbitumen may be effected and the resistance of the coating todisplacement or stripping by water improved by treating the aggregatewith small amounts of a water-soluble soap of a fatty acid in conmotionwith a water-soluble salt of a polyvalent heavy etal or activator. Foroptimum results with these reagents, the relative amounts of the tworeagents must be carefully adjusted. Thus, when a divalent heavy metalis used as activator, the amount of soap used should be substantiallyone mole per mole of activator; with a trivalent metal, between one andtwo mole of soap per mole of activator. Use of larger amounts of soapthan this diminishes the effect obtained, and this diminution of eifectincreases with excess of soap over the proportions given until, when theamount of soap becomes equivalent to the activator, i. e., two moles ofsoap per mole of divalent metal or three per mole of trivalent metal,the beneficial effect of the reagent substantially disappears.

The above method has the disadvantage that the relative amounts of soapand polyvalent heavy metal activator "ice of excess soap is not harmfulbut increases the cost. Furthermore the two reagents must be weighed ormeasured out and added to each batch, as neither is soluble in the oilor bitumen; while this disadvantage may be partially overcome underfavorable conditions by using, in place of the soap, a fatty aciddissolved in the oil or bitumen, this expedient is effective only underfavorable conditions of low moisture content of the aggregate, adequateand efficient mixing, etc. Under conditions which are not at all severe,such as appreciable amounts of water and/or facilities for onlymoderately eflicient mixing, fatty acids appear not to be sufficientlysoluble in water to reach and react with the heavy metal ion to therequired extent, and if added directly to the mixture or dissolved inthe oil or bitumen, are practically without effect.

Another important disadvantage of the above method is that a heavypolyvalent metal salt must be used with the soap. Furthermore, it hasbeen found that while some limestones appear capable of adsorbing orreacting with polyvalent heavy metal ions and accordingly respond tosome degree to the above method, a great many others do not,and withthese it is diflicult or impossible to obtain a good coating by theabove method. Also, since the foregoing method is not in generalsatisfactory with limestone, a great many natural mixed aggregates suchas gravels containing both siliceous and calcareous particles will haveonly a portion of the particles coated.

In addition to the use of polyvalent fatty acid soaps in bitumens asmineral aggregate coating agents, certain organic nitrogen compounds,such as those obtained by reacting a polyamine with a fatty acid underconditions to form essentially amides, have been used for this purpose.However, although amide-amine type asphalt additives are effectivecoating agents for acidic mineral aggregates complete amidation ofarnine soaps of carboxylic acids such as that produced by hightemperature treatment of a fatty acid affording material with an amineresults in the production of a bitumen additive with reducedeffectiveness for the coating of acidic mineral aggregates such as sandand gravel. It is a primary object of this invention to avoid theformation of amides in the preparation of the fatty acid-amine typeadditive for bitumens and thereby retain the effectiveness of theadditive in fortifying the coating material for application to acidicaggregates. Another object of the present invention is to provide acoating composition for acidic and alkaline mineral aggregates whichwill not be stripped therefrom by aqueous liquids. Still another objectof the invention is to provide a coating composition for acidic andalkaline mineral aggregates which can be supplied without the necessityof drying the mineral aggregate and which will adhere thereto even in awet condition. Another object of the invention is to avoid theproduction of a preponderance of amido groups in the fabrication offatty acidamine type bitumen additives. Still another object of theinvention is to produce a heat-stable fatty acid-amine type bitumenadditive. A further object is to produce a bitumen additive ofsufficiently low viscosity to be pumpable at ambient temperatures, thusto facilitate transfer of the additive and to facilitate theincorporation thereof in bitumen materials.

In accordance with the present invention, bitumens,

such as for examples, road oils and asphalts having im- .the productobtained by reacting a mixture of aliphatic polyamines having from 2 to6 amino groups and having from 2 to about 20 carbon atoms per moleculeand consisting essentially of at least 75%, that is from 75% to about95%, by weight of at least one alkylene polyamine having at least oneprimary amino group permolecule thereof and from about 5% to about 25%of an alkyl free of amido groups is obtained. Since amidation of aminesoaps is brought about by the loss ofwater at high temperatures, thereaction of the aliphatic polyamine with the aforementionedpropane-insoluble fraction is carried out at temperatures below about240 F., that is, in the range of from about 180 F. to about 240 F.,preferably from about 200 F. to about 230 F. for a period of time notlonger than about 0.25 to 1.0 hour. An excess of the mixed polyaminesover the stoichio'm'etric requirement for reaction with thepropane-insoluble fraction is used. Thus, in general, from about 5% toabout 50% excess of mixed polyamines is desirable.

. The reaction product of the propane-insoluble material With the mixedpolyamines, when diluted with a hydrocarbonoil, preferably an aromatic.hydrocarbon-rich hydrocarbon oil in an amount of from about 10% to about200% based on the weight of the reaction product, provides -aconcentrate of the reaction product which is pumpable at ambienttemperatures, thus making possible the transfer of'the additive productand dispersion thereof in bitumen coating material at ambienttemperatures and thus avoiding the necessity of lowering the viscositythereof by heating. Hence, amide formation is thereby minimized inhandling the additive. On the other hand,

reaction products of the propane-insoluble fatty acid affording materialwith either the non-substituted alkylene polyamine alone or with thealkyl substituted alkylene I,

polyamine alone even when diluted with an aromatic hydrocarbon-richhydrocarbon oil at a 1:1 ratio of diluent to reaction product is tooviscous to pump and approaches a semi-solid with respect to consistency.

The propane-insoluble fraction obtained in the propane extraction ofcrude fatty materials of the type above described contains, in' additionto fats and fatty acids, esters of fatty acidsv and sterols; Thesepropane-insoluble fractions which are obtained as residue of the orderof about 0.2% to about 10%, by weight, contain most of the color bodieswhich are present in the crude fatty materials, and because of theirvery dark color, are referred to in commerce as Ebony Fats. Theproperties of representative samples'of the propane-insoluble residuesobtained from animal fats and from vegetable oils, on a Water-freebasis, are approximately as follows:

Residue Residue Property from from Animal Vegetable Fat Oil Viscosity,Seconds Saybolt at 100 F- 6, 500 930 Viscosity, Seconds Saybolt at 130 F1, 860 430 Viscosity, Seconds Saybolt at 210 F 300 100 Ash. WeightPercent"; 1. 3 06 .A. P. I. Gravity degrees 10 16 Acidity A; S. T. M.(D-664) Mg. KOH/gm 41 ,63 Pentane Insoluble, Weight Percent. 2 6 2Benzene Insoluble; Weight Percent 7 0 Saponification Number 190 I 170Fatty Acid 20 31 Iodine Number- 58 0 The above properties are, ofcourse, merely illustrative, and it should-be understood that both theamount and the property of the propane-insoluble residues depend uponthe nature of the crude fatty material extracted and -pentaalkyldiethylene triamine.

.of alkyl-.substituted alkylene, polyamines containing no tation of avegetable oil. The Hodag Fat #3 had an equivalent weight of 488. Theterm crude as used herein means that the color bodies and othermaterials, insoluble in 6 to 30 volumes of the propane at about F. toabout F. have not been removed regardless of whether or not the fattymaterial has been destearinized.

The method of fractionating the animal, marine andvegetable fattymaterials with propane to obtain Ebony Fat is well known to thoseskilled in the art and one example thereof is commonly referred to asthe Solexol Process, currently and commercially used and'described inIndustrial and Engineering Chemistry of February 1949, page 280. Thesystem for effecting such extractive fractionation is described indetail in U. S. 2,505,338, and U. S. 2,521,234. For most crude animalfats,marine oils and vegetable oils, and similar fatty materialsineluding acids split from such fats, thefractionation conditions areemployed which give a propane-insoluble residue of about 1%, i. e.,about 0.2% to about 2%, although in somecases such residues may be aslarge as 5% or even 10%.

The major part, that is, at least 75% by weight, of

the polyamine reactant employed in preparing the additive of the presentinvention is an aliphatic polyamine, par

,ticularly an alkylen'e polyamine containing at least one ethylenepropylene tetramine, tetraethylene pentamine, tetrabutylene pentamine,diethylene dipropylene penta-.

mine, butylenediamine, dihexylene triamine, and the like, or mixturesthereof. For example, a suitable polyamine product as the majorpolyaminecomponent of the polyamine mixed reactant is a crude diethylenetriamine containingminor amounts of ethylene diamine and triethylenetetramine. :Other suitable polyamines include those having the generalformula RNH(CH2)3NH2 in which R is preferably a C10 to CHIS aliphaticchain, and which are obtained by condensing the suitable amine withacrylonitrile. and hydrogenating to the corresponding diamine.

Commercially-available polyamines of this type are those marketed byArmour and Company as Duomeens, whichare prepared by the condensation'of a dodecyl (coco) amine or an octadecyl (tallow) amine withacrylonitrile', followed by hydrogenation to the corresponding diamineproduct; these products are marketed as Duomeen C and Duomeen T,respectively. 7 V

The alkyl substituted alkylene polyamines are characterized by having noprimary amino nitrogen atoms and as indicated above constitute the minorfraction of the total aminereactant mixture, that is, 5% to about 25% byWeight of the total polyamines. Examples 'of these, suitable forincorporation in the amine mixture are alkyl polyethylene polyaminescontaining no primary amino nitrogen, such asdialkyl, trialkyl,tetraalkyl and Another suitable class primary amino nitrogen atomsarethe alkyl substituted ethylene diamines, such as dialkyl, trialkyl, andtetraalkyl ethylene diamine. Particularly suitable are the methylasubstituted diamines such as tetramethyl ethylene diamme.

In the preparation of-the, Ebony Fat and polyamine reaction product, itis preferable, although not essential, that the Ebony Fat befirstdehydrated .to obtain an essentially Water-free product, or.aproduct having not more than about 0.5 %water. This can be readily ac-.complished by diluting the Ebony Fat with. from about 10% to about 200%of a suitable hydrocarbon solvent,

preferably a solvent rich in aromatic hydrocarbons, and by heatingthe'diluted mixture at a temperature of about 210 F. to 290 F. whilestirring and/or blowing with air or other suitable gaseous medium untilthe water content has been reduced to the desired value. Following thedehydration step the Ebony Fat oil mixture is cooled to a temperaturebelow about 150 F., preferably by the continued inert gas blow such asfor example a passage therethrough of cold air. If the Ebony Fatcontains an undesirable amount of contaminants, they can be removed bypermitting the hot dehydrated solution to settle, and decanting thediluted solution of purified Ebony Fat. If desired, the diluent may beremoved from the dehydrated Ebony Fat by suitable means, such as bydistillation under vacuum; however, We prefer to react the diluted EbonyFats with the polyamines.

Aromatic-rich hydrocarbon solvents suitable for this purpose arepreferably those having boiling points above about 220 F. at atmosphericpressure, for example, from about 220 F. to about 600 F., and includesmononuclear aromatic hydrocarbons or condensed ring aromatics, such asnaphthalenes and mixtures of the higher boiling mono-nuclear aromatichydrocarbons and polynuclear aromatic hydrocarbons.

A preferred source of mixed aromatic hydrocarbons, suitable for thepurpose, is a light catalytic cycle stock obtained from a powdered or afluid-type catalytic-type hydrocarbon cracking operation in which gasoil or heavier hydrocarbons are cracked at a temperature of 800 F. to1050 F. under a pressure of about atmosphere to 50 pounds per squareinch, in the presence of suitable fluid or powdered catalyst, such asfor example silica-alumina, silica magnesia, and other well-knowncracking catalysts. A method of conducting a fluidized crackingoperation is described in U. S. 2,341,193, issued to Fred W. Scheineman,February 8, 1944. Fractions from the process heavier than gasoline,depending upon their boiling range, are commonly referred to as lightcatalytic cycle stock, heavy catalytic cycle stock and catalytic recycleresid, which usually are cycled to cracking. A light catalytic cyclestock particularly well suited as .a diluent for the dehydration of theEbony Fat is a fraction having an aromatic content of at least about 40%and a distillation range between about 425 F. and 560 F. A typicalanalysis of a suitable light catalytic cycle stock shows the material tobe composed substantially of about 10% normal C12 to C20 parafi'ins,about 45% of other paraflins, and naphthenes, about mono-nucleararomatics, which are mainly monoand hexa-alkylated benzenes, and about40% polynuclear aromatics, which are mainly alkyl naphthalenes, largelymethylated naphthalenes. While we prefer to use a light catalytic cyclestock of the type described, hydrocarbon fractions from other catalyticconversion processes or thermal hydrocarbon conversion processes aresuitable, provided they have an aromatic content of at least about 20%,and a distillation range of above about 220 F. If desired, a part of.the bitumen coating material, if a road oil, may be used as diluent forthe Ebony Fat for the dehydrating operation.

The dehydrated Ebony Fat, preferably but not necessarily in solution inthe light catalytic cycle stock or other suitable diluent, is reactedwith the polyamines in the ratio by weight of from about 20:1 to about5:1, and preferably in a ratio of from about 12:1 to about 5:1 Ebony Fato the mixture of polyamines, at a temperature below about 240 F. andpreferably from about 200 F. to about 230 F., for not more than aboutone hour. If desired, the polyamines may be added to the Ebony Pat inthe form of a dispersion in a hydrocarbon oil. By conducting thereaction in the manner herein described, an effective stable coatingagent additive essentially free of amido groups is obtained.

The preparation of polyamine-Ebony Fat reaction products is illustratedby the folowing examples:

EXAMPLE I To a mixture containing 244 parts by weight of Ebony Fat, thatis, Hodag (#3) Process Fat having an equivalent weight of 488 dispersedin 208 parts by weight of light catalytic cycle stock diluent was added36 parts by weight of tetramethylethylened-iamine having an equivalentweight of 5 8. The reaction mixture was mixed by means of a mechanicalstirrer at a temperature of 230 F. for a period of one hour after whichadditional light catalytic cracking cycle stock was added to thereaction mixture to adjust the finished additive to a 50% (by weight)active ingredient content.

EXAMPLE II A part of the reaction mixture prepared in Example I wasstirred for an additional 45 minutes at 300 F. to determine the effectof higher temperature on the coating properties of the primary aminonitrogen-free reaction product with the Ebony Fat.

EXAMPLE III To a mixture of 244 parts by weight of the same Hodag #3Process Fat used in Example I dispersed in 219 parts by weight of lightcatalytic cycle stock diluent was added 25 parts by weight of a 75%aqueous solution of ethylenediamine having an equivalent weight of 40,that is, 18.75 parts by Weight of polyarnine reactant. Contact of thereactants at a temperature of 230 F. was maintained for a period of onehour and diluent was added to provide a 50%50% mixture of activereaction product and diluent.

EXAMPLE IV A part of the 50% diluted reaction mixture of Example III wasstirred and reheated for a period of 45 minutes at a temperature of 300F.

EXAMPLE V To 244 parts by weight of Hodag (#3) Process Fat dispersed in204 parts by weight of the light catalytic cycle oil diluent was added amixture consisting of 27 parts by Weight of a 75% aqueous solution ofethylenediamine and 13 parts by weight of tetramethylethylene' diamine.The reaction mixture was processed in the same manner as Examples I andIII.

EXAMPLE VI A part of the reaction product obtained in Example V wasprocessed as Examples II and IV by heating for a period of 45 minutes,at 300 F.

The results of coating tests of samples of the above reaction productadditives at 1.0% (by Weight) concentration of active EbonyFat-polyamine soap, that is, 2.0% concentration of the diluted additiveare given in the table below.

While we have not been able to determine definitely the composition ofthe Ebony Fat-polyamine reaction product, we believe the reactionproduct comprises essentially the amine soaps of the fatty acidscontained in the Ebony Fat, together with unreacted esters and alcohols.i. e., sterols.

The asphalt component of the herein described composition may be anybitumen which is useful for the coating of mineral aggregates used inthe making'of roads, hi hways, etc., or for the coating of othermaterials or surfaces Where a water-resistant bond between the surfaceand the asphalt is advantageous or necessary. The term asphalt asemployed herein is intended to be synonymous with bitumen and to cover aliquid, semi-solid, or solid plastic bituminous material of the typeemployed in making or surfacing of highways and/o-r pavements, caulkingagents, sealing compounds, water impervious paints, roofing materials,etc. Such asphalt or bituminous materials are mixtures of hydrocarbonsof natural or pyrogenous origin, and are usually derived from petroleumor coal but may occur as such in nature. Asphalts may be derived asdistillation resids or cracking resids with or without oxidation byair-blowing or by catalytic oxidation, A specific example of a liquid,asphalt of the type commonly em- Fat-polyarnine reaction products inenhancing the adployed in the preparation of highways, etc., is apetroleum residuum fluxed with a light aromatic diluent boiling in therange of 400 F. to 700 F. 'to give a cut-back product of the followingspecifications:

' Cutback asphalt Flash, F. (T. O. C.) NLT 150. Viscosity, Furol at 140F 100-200.

. ASTM distillation:

1 Not less than. a Not more than.

-Normally solid paving asphalts of the m 200 pene- 'tration gradescommonly used in road building fall within the following specification:

Penetration of residue at 77 F Not less than -75.

percent of original penetration.

The efiectiveness of the herein described Ebony hesion of asphalts towet mineral aggregates is detera mined by subjecting blends of asphaltsand the described reaction products to the following test.

In preparing the samples of asphalt for testing the coating efliciencyof the fortified asphalt samples, diluted 40 additive prepared in theabove examples sufficient to provide 1.0% (by weight) concentration ofactive Ebony -Fat-polyamine component in 'the asphalt was mixedthoroughly with the asphalt. Twenty grams of Ottawa sand and 20 grams of20 to 35 mesh limestone were separately weighed into 2-ounce containersand covered with one-half inch of distilled water. One gram of theasphalt containing 1% of the additive was floated on the water. Themixture was shaken for 30 seconds and the extent of coating wasdetermined by visual inspection. The asphalt used in these tests was aliquid medium curing asphalt of the above described type and isdesignated as MC-2 grade. This test is designated as the ModifiedColorado Coating Test. A coating of 80% in this test is consideredadequate coating efiiciency to satisfy the most severe servicerequirements for the coating of wet aggregates with bitumen material.

The results of the tests are tabulated below, The asphalt coating agentwas a liquid asphalt, that is, a cutback asphalt of the above typedesignated as medium curing-2 grade.

1 Visual examination at ambient temperatures.

The results in the table show the superiority of the asphalt containingthe mixed amines (Example V) Thus, this diluted additive was very fluidat ambient temperatures and submitting the additiveto secondary heatingat a temperature of 300 F. indicated no deleterious eifect on theadditive With respect'to its efliciency as an asphalt additive, i. e.,the coverage was 95% before and after heating at 300 F. for 45 minuteswhen the asphalt fortified therewith was used for coating limestone;When this asphalt Was used to' coat sand the decrease in coatingefliciency as .a result of 'thesecondary heating step was very small, i.e., from 95% coverage to coverage.

On the other hand, the additive prepared in Example I p and Example II,i. e., the reaction product of Hodag (#3) Process Fat withtetramethylethyle'ne diamine alone as the additive was not satisfactoryeven though heated only to a temperature of 230 F. in the preparationthereof and was not satisfactory when given secondary heating at- 300 F.Since the polyamine reactant contains no primary amino nitrogen, noamide was formed by the secondary heating. This is indicated by nochange with respect to coating both sand and limestone as produced bysecondary heating. The reaction product of the Hodag (#3) Process Fatwith this polyamine showed a very high viscosity, i. e., that of a stiffliquid. The efiiciency of the asphalt fortified with ethylene diaminealone is shown in Examples III and IV. The sample of additive which hadbeen subjected to a maximum temperature of 230 F. showed acoatingefiiciency of for the two types of wet aggregate, Heating the additiveto.a temperatureof 300 F. before incorporation in the asphalt sampleresulted in a decided reduction of the coating efiiciency of the asphaltwith respect to coating sand, the percent coated decreasing from 95 to50%. Likewise, there-was a slight decrease in the coating efliciency ofthe asphalt with respect to limestone when the additive was heated to300 F. prior to incorporation in the asphalt. I

Having thus described our invention, we claim: 7

1. The proces of preparing an additive suitable for use in bitumencoating material, which process comprises reacting in a reaction zonefor a period of time of from about A to about 1.0 hour. at a temperaturewithin the range of from about 180 F. to about 240 F. a mixture Fat,which Ebony Fat is characterized as the pro-' pane-insoluble residueobtained in the solvent extraction of a crude fatty material selectedfromthe class consisting of crude animal fats, fatty oils, andfatty1acids, crude vegetable fats, fatty oils, and fatty acids,andmixtures thereof with liquified propane, said insoluble residue beinginsoluble in 6 to 30 volumes of propane at a temperature of from about140 F. to about F. and

constituting from about 0.2% to about 10% of the crude fatty materialfrom which said insoluble residue is extracted, the totalalkylene'polyamines in said reaction zone being in exces of thestoichiometric requirement for reaction with the Ebony Fat in saidreaction zone.

2. The process as described in claim 1 wherein the Ebony Fat isdehydrated to a water content of not more than about 0.5% before contactwith the alkylene polyamine components of the reaction mixture.

3. The process as described in claim 1 wherein the reaction of the EbonyFat with alkylene polyamine mix ture is carried out in the presence of ahydrocarbon oil diluent.

4. The process as described in claim 1 wherein the primary aminogroup-containing alkylene polyamine is ethylene diamine. V V

5. The process as described in claim 1 wherein the alkyl substitutedalkylene polyamine is tetramethylethylene diamine.

6. The method of preparing a hydrocarbon-oil diluted reaction product,essentially free of amido groups, suitable for use as a bitumenadditive, which comprises forming a homogeneous mixture of Ebony Pat inan aromatic hydrocarbon-rich hydrocarbon solvent boiling in the range offrom about 220 F. to about 600 F., dehydrating said mixture to a watercontent of less than about 0.5% based on the Ebony Eat content of saidmixture, reacting in a reaction zone, a mixture of alkylene polyaminesconsisting essentially of at least 75% by weight of at least onealkylene polyamine having from 2 to 6 amino groups per molecule, atleast one of which is a primary amino group and from about 5% to about25% of at least one alkyl-substituted alkylene polyamine, none of theamino groups of which are primary amino groups, with the Ebony Fat inthe dehydrated mixture of Ebony Fat and hydrocarbon oil at a temperaturewithin the range of about 180 F. to about 240 F., for a period of fromabout hour to about 1.0 hour, the total alkylene polyamines in saidreaction zone being in excess of the stoichiometric requirement forreaction With the Ebony Pat in said reaction zone, said Ebony Fat beingthe propane insoluble residue obtained in the solvent extraction of acrude fatty material selected from the class consisting of crude animalfats, fatty oils, and fatty acids, crude vegetable fats, fatty oils andfatty acids and mixtures thereof, with liquified propane, said insolubleresidue being insoluble in 6 to 30 volumes of propane at a temperatureof from about 140 F. to about 190 F., and constituting from about 0.2%to about 10% of the crude fatty material from Which said insolubleresidue is extracted.

7. The bitumen additive consisting essentially of 10 Ebony Fat-alkylenepolyamine reaction product produced as described in claim 1.

8. A bitumen composition comprising a major proportion'of a bitumen andfrom 0.25% to about 5% of 5 the bitumen active additive dispersed inhydrocarbon diluted reaction product obtained by the method described inclaim 6.

9. A roadway construction material comprising mineral aggregates admixedwith a coating composition con- 10 sisting essentially of a majorproportion of a normally liquid bitumen and from about 0.25% to about5.0% of a heat-stable reaction product obtained by reacting Ebony Fatwith a mixture of alkylene polyamines having from 2 to about 6 aminogroups per molecule and consisting essentially of at least one alkylenepolyarnine having at least one primary amino group in an amount of atleast 75% by weight of said mixture of alkylene polyamines and fromabout 5% to 25% by Weight of at least one alkyl-substituted alkylenepolyamine containing no primary amino group, at a temperature within therange of from about 180 F. to about 240 F. for a period of time of fromabout one-quarter hour to about one hour. 10. The process as describedin claim 1 wherein the primary amino group-containing alkylene polyamineis ethylene diamine and wherein the alkyl substituted a1- kylenepolyamine is tetramethylethylene diamine.

References Cited in the file of this patent UNITED STATES PATENTS2,049,467 Mnookin Aug. 4, 1936 2,201,041 Katz May 14, '1940 2,386,867Johnson Oct. 16, 1945 2,438,318 Johnson Mar. 23, 1948 2,508,924 Mertenset a1 May 23, 1950 2,521,234 Leaders et a1. Sept. 5, 1950

1. THE PROCESS OF PREPARING AN ADDITIVE SUITABLE FOR USE IN BUTIMENCOATING MATERIAL, WHICH PROCESS COMPRISES REACTING A REACTION ZONE FOR APERIOD OF TIME OF FROM ABOUT 1/4 TO ABOUT 1.0 HOUR AT A TEMPERATUREWITHIN THE RANGE OF FROM ABOUT 180* F. TO ABOUT 240* F. A MIXTURE OFPOLYAMINES HAVING FROM 2 TO ABOUT 6 AMINO GROUPS PER POLYAMINE MOLECULE,SAID MIXTURE CONSISTING ESSENTIALLY OF AT LEAST 75% BY WEIGHT OF ATLEAST ONE ALKYLENE POLYAMINE CONTAINING AT LEAST ONE PRIMARY AMINO GROUPAND FROM ABOUT 5% TO ABOUT 25% BY WEIGHT OF AT LEAST ONEALKYL-SUBSTITUTED ALKYLENE POLYAMINE CHARACTERIZED BY HAVING NO PRIMARYAMINO GROUP IN THE MOLECULES OF SAID ALKYL-SUBSTITUTED ALKLENEPOLYAMINE, WITH "EBONY FAT," WHICH "EBONY FAT" IS CHARACTERIZED AS THEPROPANE-INSOLUBLE RESIDUE OBTAINED IN THE SOLVENT EXTRACTION OF A CRUDEFATTY MATERIAL SELECTED FROM THE CLASS CONSISTING OF CRUDE ANIMAL FATS,FATTY OILS, AND FATTY ACIDS, CRUDE VEGETABLE FATS, FATTY OILS, AND FATTYACIDS, AND MIXTURES THEREOF WITH LIQUIDIFIED PROPANE, SAID INSOLUBLERESIDUE BEING INSOLUBLE IN 6 TO 30 VOLUMES OF PROPANE AT A TEMPERATUREOF FROM ABOUT 140* F. TO ABOUT 190* F. AND CONSTITUTING FROM ABOUT 0.2%TO ABOUT 10% OF THE CRUDE FATTY MATERIAL FROM WHICH SAID INSOLUBLERESIDUE IS EXTRACTED, THE TOTAL ALKYLENE POLYAMINES IN SAID REACTIONZONE BING IN EXCESS OF THE STOICHIOMETRIC REQUIREMENT FOR REACTION WITHTHE "EBONY FAT" IN SAID REACTION ZONE.
 9. A ROADWAY CONSTRUCTIONMATERIAL COMPRISING MINERAL AGGREGATES ADMIXED WITH A COATINGCOMPOSITION CONSISTING ESSENTIALLY OF A MAJOR PROPORTION OF A NORMALLYLIQUID BITUMEN AND FROM ABOUT 0.25% TO ABOUT 5.0% OF A HEAT-STABLEREACTION PRODUCT OBTAINED BY REACTING "EBONY FAT" WITH A MIXTURE OFALKYLENE POLYAMINES HAVING FROM 2 TO ABOUT 6 AMINO GROUPS PER MOLECULEAND CONSISTING ESSENTIALLY OF AT LEAST ONE ALKYLENE POLYAMINE HAVING ATLEAST ONE PRIMARY AMINO GROUP IN AN AMOUNT OF AT LEAST 75% BY WEIGHT OFSAID MIXTURE OF ALKYLENE POLYAMINES AND FROM ABOUT 5% TO 25% BY WEIGHTOF AT LEAST ONE ALKYL-SUBSTITUTED ALKYLENE POLYAMINE CONTAINING NOPRIMARY AMINO GROUP, AT A TEMPERATURE WITHIN THE RANGE OF FROM ABOUT180* F. TO ABOUT 240* F. FOR A PERIOD OF TIME OF FROM ABOUT ONE-QUARTERHOUR TO ABOUT ONE HOUR.